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United States Patent 3,123,595 REACTIVE DYESTUFFS Hugo Brugger andHermann Burkhard, Basel, Switzerland, assignors to Sandoz Ltd. (alsoknown as Sandoz A.G.), Basel, Switzerland No Drawing. Filed Apr. 12.,1960, Ser. No. 21,620- Claims priority, application Switzerland Apr. 17,1959 11 Claims. (Cl. 260151) This invention relates to reactivedyestuffs which contain at least one 2.3-dihalogenopropyl group asreactive substituent. The process for their preparation consists intreating with halogen or a halogen-yielding agent, organic dyestuffs orcompounds containing substituents capable of dyestuff formation andpossessing at least one allyl group, upon which the reaction products,when they contain radicals of organic compounds with substituentscapable of dyestuff formation, are converted into dyestuffs by asuitable reaction.

A special mode of operation of the process consists in reacting with2.3-dihalogenopropylamine or 1.2.3-trihalogenopropane, organic dyestuffsor compounds containing a substituent which is capable of dyestufr"formation and possesses at least one acid halide or acid amide group,whereupon the reaction products, when they contain radicals of organiccompounds with.substituents capable of dyestulf formation, are convertedinto dyestufis by a suitable reaction.

The neW process is applicable with all classes to dyestuffs, viz.:monoazo and polyazo dyestuffs which may contain metallizable groupingsor metal atoms in complex combination, e.g., chromium, cobalt, nickel orcopper atoms, anthraquinone dyestuffs, phthalocyanine dyestuffs, nitrodyestufis etc.

The azo dyestuffs containing metallizable groupings can be metallizedafter condensation or, alternatively, they can ze reacted with the fiberin the metal-free form and the dyeings aftertreated with ametal-yielding agent.

The 2.3-dihalogenopropyl group can be connected to the dyestuif moleculeeither directly or through a bridge member. Suitable bridge members are,e.g., O--, S, NH, -CO, NHCO, but

is preferable; in which case NH is linked to the 2.3- dihalogenopropylgroup.

In accordance with the definition it is possible to arrive at dyestuffscontaining at least one 2.3-dihalogenopropyl group by startingfromcompounds containing at least one allyl group and a substituent which iscapable of dyestufi formation either directly or after a suitablereaction. The azo coupling has an important bearing on the reactiongiving the final dyestuffs. It can be effected by treating compoundscontaining at least one allyl group and a nitro or readily saponifiableacylamino group with halogen (chlorine, bromine) or a halogen-yieldingagent (benzeneor 4-methylbenzene-l-sulfonic acid dichloramide, chloroorbromosuccinirnide), reducing the nitro group or saponifying theacylamino group, diazotizing the intermediate product and coupling thediazo compound with a coupling compound to give the dyestuif.

Again, compounds which have at least one allyl group and a carbon atomcapable of coupling can be reacted with halogen or halogen-yieldingagents to give an intermediate product for use as coupling compound. Thehalogenation is carried out advantageously in an organic medium (CS CHClCCL, tetrachlorethane, benzene,

Itoluene, chlorobenzene, glacial acetic acid and at low temperatures,e.g., between 0 and 30 C. It follows that the diazo compound of a diazocomponent containing a 2.3-dihalogenopropyl radical can also be coupledwith 3,l23,595 Patented Mar. 3, 1964 a coupling component which likewisecontains a 2.3-dihalogenopropyl radical.

The dyestuffs employed in the special mode of operation of the processas described above can be selected from any class of dyestuffs. Theymust contain at least one acid halide or acid amide group, e.g., asulfonic acid halide or carboxylic acid halide group, preferably asulfonic acid chloride or carboxylic acid chloride group, or a sulfonicacid amide or carboxylic acid amide group. The reaction of the acidhalide group with 2.3-dihalogenopropylamine, e.g., 2.3-dichloroor2.3-dibromopropylamine, is conducted in aqueous, aqueous-organic ororganic medium and preferably in presence of acid-binding agents and atlow temperatures, e.g., between 0 and 70 C. The reaction of the acidamide group with 1.2.3-trihalogenopropane, e.g., 1.2.3-trichloro-,1.2.3-tribromo or l-bromoor 1-iodo-2.3-dichloropropane, can also becarried out in aqueous medium. As the 1.2.3-trihalogenopropanes areinsoluble in water it is, however, advantageous to work inaqueous-organic or in organic medium and preferably in presence ofacid-binding agents. The temperature can be varied within wide limits tosuit the reactivity of the 1.2.3-trihalogenopropane, e.g., from 0 to 150C., and pressure can be applied if necessary. The addition of wetting,emulsifying or dispersing agents can accelerate the rate of reaction.

The intermediate products, which contain substituents capable ofdyestulf formation directly or after suitable conversion and in additionan acid halide or acid amide group, can also be reacted with2.3-dihalogenopropylamine or 1.2.3-trihalogenopropane. The dyestuif isthen formed from the reaction product immediately or after it has beenconverted, e.g., the nitro group reduced to an amino group when a diazocomponent is involved, in which case it is important to ensure that thetrihalogenopropyl group is not damaged during the formation of thedyestuif.

On completion of condensation or coupling the solution or suspension isneutralized if desired, and the re active dyestuif is salted out withsodium or potassium chloride or precipitated with acid. It issubsequently filtered with suction, washed and dried.

The water-soluble reactive dyestuffs of the invention which contain atleast one 2.3-dihalogenopropyl radical, are suitable for the dyeing,padding and printing of fibers of vegetable and animal origin, fibers ofregenerated cellulose, casein fibers, animalized cellulosic fibers,synthetic polyamide fibers, mixtures of these fibers, and leather. Ifnecessary the dyeings and prints are subjected to an alkaline aftertreatment at high temperatures and then soaped. They possess goodfastness to light, washing, milling and perspiration.

The water-soluble reactive dyestuffs of the invention reserve acetate,triacetate. polyethylene terephthalate, polyvinyl chloride andpolyacrylonitrile fibers.

The water-insoluble reactive dyestuffs of the invention are suitable fordyeing secondary cellulose acetate, cellulose triacetate andpolyethylene terephthalate fibers and especially synthetic polyamidefibers in dyeings fast to wet treatments.

In the following examples the parts and percentages are by weight andthe temperatures in degrees Centigrade.

Example 1 In a mixing vessel equipped with a thermometer, refluxcondenser and charging funnels, parts of 3-nitrobenzene-Lsulfonic acidamide are suspended in parts of Water and parts of ethyl alcohol withthe addition of 20 parts of sodium hydroxide, which brings about partialdissolving. 65 parts of allyl bromide are added and the mixture heatedfor 23 hours with reflux. On cooling, it is adjusted to pH 7 and thegray-yellow,

3 crumbly mass filtered off. On recrystallization from carbontetrachloride, the product is obtained in the form of white needles witha melting point at 7578.

40 parts of the aforementioned product are dissolved in 300 parts ofcarbon disulfide and chlorinated at with dry chlorine gas until thegreen-yellow colour in the vessel indicates that the reaction iscompleted. The product is recrystallized form 30% alcohol. lts meltingpoint is 95-98, its chlorine content 22.3% (found), 22.7% (calculated)The next step, reduction, is begun by suspending 25 parts of iron powderin 160 parts of ethyl alcohol and etching the metal in minutes at 45-50with 2.5 parts of glacial acetic acid. Immediately afterwards, 30 partsof 3-nitrobenzene-1-sulfonic acid-(2.3-dichloro)-propylamide are addedand the nitro group reduced by boiling for 16 hours with reflux. Oncooling to room temperature the excess iron powder is filtered off andthe red-brown reaction mixture diluted with 500 parts of water. Anondiazotizable substance is separated by acidification with 100 partsof concentrated hydrochloric acid. After filtration the amine can beisolated as a hydrochloride by evaporation of the filtrate. Onrecrystallization the pure hydrochloride is obtained. M.P. 203206(decomposition), chlorine content 33.2% (calculated), 32.1% (found).

An amount of the chlorohydrate equivalent to 11.3 parts of3-aminobenzene-l-sulfonic acid-(2.3'-dichloro)- propylamide is stirredinto 40 parts of water and 10 parts of 30% hydrochloric acid anddiazotized by the addition of a solution of 2.8 parts of sodium nitritein 10 parts of water at 0-3. After about 10 minutes the excess nitriteis destroyed with amidosulfonic acid and this solution is run into aneutral solution at 3-5 of 13.2 parts of 1-(2.5-dichloro)-pl1enyl 3methyl-5-pyrazolone-4'- sulfonic acid in 200 parts of water. The pH isadjusted to 44.5, e.g., with sodium acetate solution, upon whichcoupling takes place immediately to give a yellow dyestuff which isprecipitated in quantitative yield. After 4 hours stirring at 0-5 theproduct is filtered off and dried at 60. It is a yellow powder whichdissolves in water with a yellow coloration and dyes Wool, silk,synthetic polyamide fibers and cellulosic fibers in yellow shades whichare fast to light, washing, milling and perspiration.

A suitable dyeing method is as follows: A dyebath is set with 5000 partsof water and 4 parts of the abovedescribed dyestuif and the pH valueadjusted to 6. 100 parts of wetted wool are entered and dyed for 1%hours at 90-100", then sodium hydroxide solution is added to bring thepH to 8.7 and dyeing continued for 30 minutes at 80-90". The dyeingobtained is removed, washed with water with a little acetic acid in oneof the Washing baths, and dried.

Example 2 14 parts of 3-aminobenzene-1-sulfonicacid-(2.3'-dichloro)-propylamide are stirred ito 18.5 parts of 30%hydrochloric acid and 50 parts of water. At 0-3 14.5 parts of 4 n.sodium nitrite solution are added and the solution stirred for a shorttime at 0-5". A second solution is prepared with 13.5 parts ofl-hydroxy-naphthalene- 3.6-disulfonic acid in 250 parts of water withthe addition of sodium carbonate, which after cooling to 3-5" isadjusted to pH 4-4.5 with glacial acetic acid and mixed with the diazosolution. The pH value of the coupling mixture is maintained at 4-4.5with sodium acetate. On completion of coupling the orange-red dyestuffis salted out, filtered with suction, again dissolved 750 parts of waterand reprecipitated, and dried.

On cotton the dyestuil gives dyeings fast to light, Washing, water andperspiration.

i Example 3 14 parts of 3-aminobenzene-l-sulfonicacid-(2.3'-dichloro)-propylamide are diazotized according to theprocedure described in Example 2. 11.2 parts ofl-hydroxynaphthalene-4-sulfonic acid are dissolved in 250 parts of waterwith the addition of sodium'carbonate and the solution adjusted to pH4-4.5 with glacial acetic acid. At about 3-5 this solution is mixed withthe diazo solution, upon which the dyestufi is precipitated. It isdissolved in 750 parts of water, reprecipitated and dried at 60.

A mercerized cotton fabric is padded with a 3% neutral solution of theabove dyestufi at 50 and an expression (pick-up) of about After drying,the padding is fixed by treatment for about 1 hour with constantagitation in a developing bath at 80-90 set with 250 parts of calcinedsodium sulfate, 15 parts of trisodium phosphate and 3 parts of sodium3-nitrobenzene-1-sulfonate per 1000 parts of the solution. The liquorratio of this bath may vary from 1:10 to 1:50. Fixation is followed bythorough rinsing in cold water, soaping at the boil, rinsing and drying.The orange-red dyeing obtained is fast to light, water, washing,perspiration, soda boiling, rubbing, and dry cleaning.

Example 4 200 parts of water and 29 parts of allylaanine are entered ina glass beaker equiped with a stirrer, thermometer, dropping funnel andpH measuring attachment. At an initial pH value of 10.3 parts of3-methyl-4-nitrobenzene-l-carboxylic acid chloride are dropped in. Soonthe pH begins to fall and solid sodium carbonate is added slowly tomaintain it at 7-8, the rate of addition being controlled so that thetemperature does not rise above 20-28. A light yellow, crumbly mass isformed which on completion of the reaction is filtered 01f. It is wellsoluble in alcohol, chlonobenzene and triohloroethylene. 'Recrystallizedfrom alcohol with the addition of active carbon, it melts at 86-88".

40 parts of the above-described carboxylic acid amide are suspended in300 parts of carbon disulfide, upon which it goes intopartial solution.On cooling to 5 it is chlorinated with dry chlorine gas until thegreen-yellow color in the vessel indicates that the reaction iscompleted. The carbon disulfide is decanted from the tough, highlyviscous substance, and the product, freed from solvent, isrecrystallized from water. Its melting point is 114-116", and thechlorine content is 24.2% (calculated) and 22.4% (found).

Reduction is initiated by suspending 25 parts of iron powder in parts ofalcohol and etching the metal at 45-50 in 10 minutes with 2.5 parts ofglacial acetic acid, following which 30 parts of3-methyl-4-nitrobenzene-lcarboxylic acid-(2'3-dichloro)-propylamide areadded and the nitro group reduced by heating for 16 hours at 75-80". Oncooling the excess iron powder is filtered off and the filtrate, with anaddition of 100 parts of concentrated hydrochloric acid, is evaporatedin vacuo. In this Way the hydrochloride of the amide is obtained as alight yellow powder.

11.5 parts of 3-methyl-4-aminobenzene-l-carboxylicacid-(2.3'-dichloro)-propylamide are stirred into 40 parts of water and15.5 parts of 30% hydrochloric acid. At 03% 13 parts of 4 11. sodiumnitrite solution are added. On diazotization the excess sodium nitriteis destroyed with amidosulfonic acid and the diazo solution at 35 is runinto a solution of 16.5 parts of l-(2'.5'-diohlorro)-phenyl-3-methyl-5-pyrazolone-4-sul-fonic acid in 200 parts of water, thepH value being adjusted to 4-4.5 with sodium carbonate. Coupling takesplace immediately to give a yellow dyestufif which is precipitated inquantitative yield. After stirring for 4 hours at 0-3 the product isfiltered off and dried at 60. It is a yellow powder which dyes Wool,silk, synthetic polyaanide fibers and cellulosic fibers from aqueoussolution in yellow shades.

A cotton fabric is printed with a paste of the following composition:

6 symbols X, Y, Z, V and Hal in the diazo component of the formula NH;30 parts of the dyestufi of this example, 100 parts of urea, 5 450 partsof 3.5% sodium alginate thickening, 6 2 parts of sodium3-nitrobenzene-1-sulfonate, 5 3 parts of sodium canbonate, 395 parts ofwater .XYCH2-CH-CH2Ha1 1000 parts 10 a1 (columns (I), (II), (III), (IV)and (V)), by the posi- Ihe prmt1sdr1ed, steamed for 10 rmnutes at102104, i of h o rinsed with cold and water, soaped at 100 w th a 0.2%soap solution, rinsed again and dried. It 1s of yellow shade andpossesses high fastness to light, water, 15 Hal washing, perspiration,rubbing and dry cleaning. group (column (VI) by the coupling componentDetails of further reactive dyestufis are set forth in the (column(VII)) and by the shade of the dyeings on wool following table. They areobtainable by the procedures for the water-soluble dyestuffs or onsynthetic polyamide described in Examples 1 to 4 and are characterizedby the fibers for the water-insoluble dyestuffs (column (VIII) Example(VIII) No. (I) X (H) Y (III) V (IV) Z (V) (VI) (VII) Coupling componentShade of Hal Position the Dyeing NH- H H Cl 3l-phenyl-3-methyl-frpyrazolone yellow. NH H H 01 4 hydroxybenzenebrovlrlnish ye ow. NH H H Cl 4 2-hydroxynaphthalene-8-sulfonic acidreddish orange. NH H H C1 4 2 amino 5 hydroxynaphthalene 7- brown red.

sulionic acid. NH H H Cl 4 2hydroxybenzene-l-carboxylic acid... yellow.NH H H Cl 3 2 hydroxynaphthalene 6.8 disulreddish fonic acid. orange. NHH H Cl 3 2-hydroxynaphthalene-G-sulfonic acid- Do. NH- H H 01 4Z-hydroxynaphthalene-sulfonic acid-.- Do. NH H H Br 3l-aminonaphthalene-4-sulfonic acid orange. NH H H Br 3Z-hydroxynaphthalene-4-sulfonic acidbluislh re NH-- H H Cl 3 1acetylamino 8 hydroxynaphtha- Do.

lene-3.6-disulfonic acid. NH- H H 01 4 1.3-dihydroxybenzene. yellow.N(CH H H Cl 4 2 benzoylamino 8 bluish thalene-3.6-disu1fonic acid. red.N(CH3) H H 01 4 4 amino l hydroxybenzene 2- brown.

carboxylic acid. NH H H C1 4 Z-amino8-hydroxynaphthalene-6- bluish red.

sulfonic acid. NH- H H Cl 4 2-hydroxynaphthalene-7-sulfonie acid.orange. NH H H Br 3 1.3-diamin0benzene-6-sulionic acid yellowtown. NH- HH Br 4 l-phenylaminonaphthalene-S-sulionic red.

8.01 23".-." CO- NH- H H Br 4 l-hyflroxynaphthalene-4.8-disu1ionicbluish red.

ac1 24 SO NH- H H Cl 3 1-hyd1roxynaphtha1ene-3.6-disulfonic orangeac1 re25 SO NH- H H Cl 3 l-hydlroxynaphthalene-4-sullonic red-orange.

3.01 26 SOg- NH- H H 01 3 1-(3-chloro)-phenyl-3methyl-5- yellow.

pyrazolone. 27 SO: NH H H 01 4 1-l1y droxynaphtha1ene-3.6.8-trisulfonicred.

aci 28 SOg- NH H H 01 3 2.4-diamino-1-methylbenzene brovfiiye ow. 29 -80NH H H Cl 3 1-dimethylamino-sulfonylamino-7- red.

hydroxynaphthalene. 30 SOr- NH- H H 01 32-hy%roxynaphthalene-3.fi-disulfonic orandgeaci re 31 SO NH H H 01 4I-aminonaphthalin-S-sulfonic acid orange, 32 C 0- NH- H CH: 01 41phenyl-3-methyl-S-pyrazoloneyellow.

2.5-disnlfonic acid. 33 SOz- NH H 80:11 C1 41-(2.5-dicl1loro)-phenyl-3-mcthyl-5- greenish pyrazol0ne-4-sulfonicacid. yellow. 34 CO- NH- H CH; 01 4l-benzoylamino8-hydr0xy-naphthabluish red.

1ene-3.6-disulfonic acid. 35 CO- NH- H CH3 Cl 4l-benzoylamino-8-hydroxy-naphthared.

lene-4.6-disulfonic acid. 36 CO NH H CH; 01 4l-benzoylamino-Bhydroxy-naphtha- Do.

lene-3.5-disulf0nic acid. 37 SO3 NH H OH 01 4l-acetylamino-S-hydroxy-naphthanavy blue.

1e1ne-3.5-disul fonic acid: Cu-Comp ex. 38 S O;- -NH NO: OH Cl 4I-acetylaruino-8-hydroxy-naphthabluish lone-3.6-disulfonic acid:Cr-Comgray,

ex. 39 SO- NH NOB OH 01 4 l-acetylarnino8-hydroxy-naphthareddish1ene-3.6-disulf0nic acid: Co-Comgray.

ex. 40 C O- NH- H CH3 Cl 4 l-hyddr0xynaphthalene-4-sulfonic red.

aci 41 SO; NH H H 01 3 l-(2.5-dichl0r0)phenyl-3-methyl-5- yellow.

pyrazolone-4-sultonic acid. 42 SO H H Cl 31phenyl3-methyl-fi-pyrazolone- Do.

2'.5'-disulfonic acid.

r e Puther the dyestuffls of the formulae:methyl-1.1'-azobenzene-3'-sulfonic acid-(2.3-dichloro)- sOaH OHpropylarnide, 20 parts of sodium dinaphthylmethanedisulfonate, 10 partsof sodium cetylsulfate and 35 parts of C N=N reddish orange anhydroussodium sulfate is ground in a roller mill for 5 48 hours. 1 part of theresulting dyestufi preparation is l v a S0311 carefully pasted with colddistilled water and dispersed by adding further water. The dispersion isrun into a (43) SOZ NH OHB CHC1 OH1C1 solution of 2 parts of asulfonated Castor oil with a degree N=N-NHO o-C orr2-o HC1C H201 CH:reddish yellow (44) S OsII O of sulfonation of 80% and 2.5 parts of 100%acetic II I 20 acid in 3500 parts of Water, the volume then being madeS0311 up to 4000 parts. 100 parts of Well scoured nylon 66 blue fabricare entered into the dyebath, the temperature increased to the boil inabout 30 minutes and maintained I at 95100 for 30 minutes. The 'dyedmaterial is then 0 NH@ 5 removed, treated for 1 hour at 100 in a bath of4000 1 parts of Water and parts of sodium carbonate, and (45) SO2 NH OHZCHC1 CH2 C1 subsequently soaped in a solution of 1.5 parts ofoctylphenylootaglycol ether in 4000 parts of water for minl so H) utesat 70, rinsed and dried. A yellow dyeing fast to 3x 3; a 3 turquoiselight, washing, water, perspiration, rubbing and sublima- 4eyanineTSO1NHCHzOHCi-CH;C1 ti-on is obtained. (6) Formulae ofrepresentative dyestuffs of the foregoing O NHz examples are: 1| Example1: 1103s -SO3H 01 Q blue C-N- SOaH H I I 0 NH Cl C=Cl-HzC-OIHO-HzCHN-O1S (47) SO2NHCH2CHClCHzCI CHa HOa'S N=N -NH(|%oH-s-oH oH01OH o1 O reddish yellow HOaS CH3 HOzS N=N-NHCOOHzOCH2OHCl--OHz-Ol t reddish yellow HOaS- CH3 N0 OH L I Example 2HO3SC N=N OH reddish yellow I (5Q) S|O2 NH CII;4 CHC1 CH2O1ClHzCClHCHzC-HNO2S HOaS SO3H OH HO I I Example 3:

110 S N=N 3 Ci -complex gray-black OH 51 N02 SOzNH-GH1OHClCHzC1 C1 H2CO1HO H2 CHNAMIS Dymg Example 52 A mixture of 35 parts of the dyestuff2-hyd-r0Xy-5- 303E 9 10 Example 4:

01 OH 3 C-N-Q-SOaH c11sI2co1Ho-H0-HNocO-N=N-o 1 Example 32:

SOQH HO C-N C1H2C-C1CH-HzCHN-OCC N=NC Example 34:

0113 no NH-OC ClHaC-OIHC-HzC-HN-OCC N=N HOaS- SOaH Example 35:

(|)Ha on NH-O 0-C 01HzC-C1HC-H2C-HNOC -N=N HOaS Example 36:

OH; Ho NH-O 0Q C1HzCOlHC-H2CHNOON=N SOaH s 0 H Example 37: Coppercomplex compound of- Example O NH2 45 (311 HO 1\IIHO 0-0113 4033 HOaSSOzH '5 g I C1H2C-C1HC H2C HN02S SOzNHCI-Iz-CHOlCHzC1 Example 46:Example 38: Chromium complex compound of 5 Copper '|(SO3H)3 Phthalomnmes O2NHO H;C HCl-C H201 OH HO NHOO-CH3 .J l l l Having thus disclosed theinventlon what we claim is: 1. Water-soluble reactive dyestuffconsisting essentially of HO3S- o (1) a dyestuif grouping selected fromthe class consisting of CIH CL-CIHC-H C-HN-Ofi (a) unmetallized monoazodyestutf grouping se- I lected from the class consisting of (i)benzene-azo-benzene groupings, Example 39: Cobalt complex compound of(ii) benzene-azo-naphthalene groupings,

(iii) benzene-azo-S-pyrazolone groupings, and F HO I]IHOC CH3 (iv)naphthalene-azo-naphthalene p s; N=N (b) chromium, copper, cobalt andnickel complexes of (a); H038 SOaH (c)1amino-Z-sulfo-4-phenylamino-anthraquinone groupings; C1H C-O1HCHOHNOS 7and (d) copper phthalocyanine sulfonic acid V 9. The copper complexcompound of the reactive dyegroupings; stufi of the formula (2) as solereactive grouping, a HO OH -OHz-(l1HCHz-Hal l I Hal N=N grouping,wherein Hal has an atomic number from H038 03H 17 to 35 inclusive; and

(3) a divalent bridge grouping connected by one of OIHEO CIHC HZC HN OZSits valences to a nuclear carbon atom of the dyestuff 1, Th hr 1 d f hgrouping (1) and by its other valence to the terminal e c Omlum comp excompoun 0 t e reacuvfi CH of the reactive grouping (2), said bridgedyestufi the formula grouping being selected from the class consistingof 01-1 7 -SO NH-, CONH, CON(OH T 00 SO N(CH N=N NHCOOOT HOaS -s03H-NHCOOH S- and N-HCO'--CH -O 2. The reactive dyestufi of the formulaO1HBC C1HC-HCHN O2S sour r10 3 CN C1HzCO1HCHzCHN-O CC N=NC I SOaH CH; 3.The reactive dyestufi of the formula 01 HO 0H3 I I CN-SO:H

C1II2G-O1HCII2CHNO o -N=NC l CH; 4. The reactive dyestufi? of theformula (1H3 Ho NI-L-OC-O o lHzG-CIHC-HzC-HN-O o- -N=N H03s- S03H 5. Thereactive dyestuif of the formula (3H3 on IFI-I-OC-O OlHzC--C1HCH2OHNO CCN=N HOaS SOaI-I 6. The reactive dyestufi of the formula (1H3 no NHOOClHzCC1HC-H GHNO CN=N -SO3H S OaI-I 7. The reactive dyestuff of theformula 11. The cobalt complex compound of the reactive dyestuff of theformula copper (S03H)3 OH HO NHOCOI-I3 phthalocya- I l I runeSOBNHCHZOHCICH2CI N=N- 8. The reactive dyestutf of the formula HOaS SO3Hi i so H GlHzO-CIHC-HzC-HN-OzS 3 References Cited in the file of thispatent UNITED STATES PATENTS 2,128,255 Krzikalla et a1 Aug. 30, 1938 0 G2,743,267 Heyna et :al Apr. 24, 1956 2,766,231 Bolliger Oct. 9, 1956 lSOZNHCHZOIIOI-CH2CI 2,824,864 Buehler Feb, 25, 1953 UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION Patent No, 3 l23 595 Maren?) 1964'.

Hugo Brugger at alo It is hereby certified that error appears in theabove numbered patent requiring correction and that the said LettersPatent should read as corrected below. I

Column l line 37- for "ze" read be -"g line =-68 ,after "acid" insert aclosing parenthesis; columns 5 and 6 Example 31 under column VII for"'aminonaphthalin" read aminonaphthalene column 6 lines 3 to l0 theleft-hand portion of the formula should appear as shown below instead ofas in the patent:

column 7 line l for 'Futher" read Further line 74 for Dying read Dyeing3 column 9 Example 36 for that portion of the formula reading:

read

SO H

Signed and sealed this 10th day of November 1964.,

(SEAL) Attestz ERNEST We SWIDER EDWARD J, BRENNER Attesting OfficerCommissioner of Patents

1. WATER-SOLUBLE REACTIVE DYESTUFF CONSISTING ESSENTIALLY OF (1) ADYESTUFF GROUPING SELECTED FROM THE CLASS CONSISTING OF (A) UNMETALLIZEDMONOAZO DYESTUFF GROUPING SELECTED FROM THE CLASS CONSISTING OF (I)BENZENE-AZO-BENZENE GROUPINGS, (II) BENZENE-AZO-NAPHTHALENE GROUPINGS,(I.I) BENZENE-AZO-5-PYRAZOLONE GROUPINGS, AND (IV)NAPHTHALENE-AZO-NAPHTHALENE GROUPINGS; (B) CHROMIUM, COPPER, COBALT ANDNICKEL COMPLEXES, OF (A); (C)1-AMINO-2-SULFO-4-PHENYLAMINO-ANTHRAQUINONE GROUPINGS; AND (D) COPPERPHTHALOCYANINE SULFONIC ACID GROUPINGS; (2) AS SOLE REACTIVE GROUPING, A